EP0572029B1 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0572029B1
EP0572029B1 EP93108671A EP93108671A EP0572029B1 EP 0572029 B1 EP0572029 B1 EP 0572029B1 EP 93108671 A EP93108671 A EP 93108671A EP 93108671 A EP93108671 A EP 93108671A EP 0572029 B1 EP0572029 B1 EP 0572029B1
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EP
European Patent Office
Prior art keywords
silver
group
mole
light
silver halide
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EP93108671A
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German (de)
English (en)
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EP0572029A1 (fr
Inventor
Kiyohito Takada
Kentaro Okazaki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP13935192A external-priority patent/JP2840500B2/ja
Priority claimed from JP13940292A external-priority patent/JP2840501B2/ja
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Publication of EP0572029A1 publication Critical patent/EP0572029A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/381—Heterocyclic compounds
    • G03C7/382—Heterocyclic compounds with two heterocyclic rings
    • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives
    • G03C7/39204—Inorganic compounds

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material, specifically to a silver halide color photographic light-sensitive material having an excellent processing performance and color reproducibility and providing stable photographic performance against compositional changes in the processing solutions of a continuous processing of a low processing solution replenishing-type, as well as having decreased sensitivity change due to aging of a coating solution and enabling a stable photographic performance to be obtained. Further, the present invention provides less desensitization stripes which are generated by pressures applied in a processing solution.
  • the process is restricted by the absorption characteristics of the cyan, magenta and yellow dyes used, i.e., how truly and in what broad range the colors can be reproduced in the color print. Where the light absorption profile of the dye is broad and undesirable side-absorptions are involved, a color turbidity is generated.
  • An example of an unnecessary side-absorption deteriorating the color reproduction is that the green color of, for example, a green leaf which is photographed on a color negative film and reproduced on a color print inclines to a brownish green color in some cases.
  • JP-A-64-553 the term "JP-A" as used herein means an unexamined published Japanese patent
  • JP-A is improved as to side-absorption in short wavelength regions compared with that of conventional dyes, but those couplers do not always have sufficient color reproducibility and there remains the problem that color developing performance is notably low.
  • the preparation and evaluation of color light-sensitive materials in which the cyan dye-forming coupler having this pyrroloazole primary nucleus is used in combination with a high silver chloride emulsion has resulted in the finding of a serious practical problem which has not been anticipated. That is, the silver halide color photographic light-sensitive material can surely provide a cyan dye image having a high color purity, but the various processing tests carried-out under retail market color lab, development processing conditions (a processing station) have revealed the problem of large changes (of the cyan dye portion) in photographic performance due to compositional changes in processing solutions.
  • JP-A-2-96150 a technique in which a high silver chloride emulsion provided with a silver bromide-localized phase and a specific processing can be combined to decrease the change in a photographic performances before and after continuous processing.
  • the results of the investigations repeated by the present inventors reveal that the change in photographic performances can certainly be reduced, but not necessarily sufficiently and further the generation of the desensitization stripes as described above can not be decreased.
  • EP-A-0 488 248 and EP-A-0 491 197 which are documents in accordance with Art. 54(3) EPC, describe a silver halide color photographic material wherein at least one silver halide emulsion layer contains at least one 1H-pyrrolo [1,2-b] [1,2,4] triazole cyan coupler which may be in the form of a bis-compound or a polymer. These documents remain silent with respect to the whole amount of calcium contained in the photographic layers.
  • An object of the present invention is to provide a silver halide color photographic light-sensitive material having a high sensitivity, excellent performance in a rapid processing and color reproduction and providing stable photographic performance due to compositional changes in processing solutions in a low replenishing process and in which a desensitization stripe is not readily generated when the continuous processing is carried out.
  • Another object of the present invention is to provide a silver halide color photographic light-sensitive material which avoids the problem of calcium being deposited on a roller during processing and in which an emulsion having less sensitivity reduction during the storage of a coating solution is used.
  • the present invention provides a silver halide color photographic light-sensitive material comprising a support and provided thereon photographic constitutional layers comprising at least one layer each of a light-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a light-sensitive silver halide emulsion layer containing a cyan dye-forming coupler, and at least one non-light-sensitive layer, wherein the above silver halide emulsion layer containing a cyan dye-forming coupler contains (i) at least one of the pyrroloazole-type cyan couplers represented by the following Formula (Ia), and (ii) (a) silver bromochloride grains having a silver chloride content of 90 mole% or more or silver chloride grains, each chemically sensitized with a gold compound or (b) silver bromochloride grains containing silver iodide in an amount of 1,0
  • the maximum amount of calcium contained in the above photographic constitutional layer is preferably 10 mg/m 2 or less, and most preferably 8 mg/m 2 or less per m 2 of the silver halide color photographic material.
  • the calcium content in the silver halide color photographic light-sensitive material depends on the calcium content in the gelatin, used primarily as a binder.
  • gelatin having a reduced calcium content is used to prevent the problem of calcium being deposited on a roller during processing and the reduction in sensitivity of an emulsion during the storage of a coating solution.
  • the use of the cyan dye-forming coupler makes it possible to use gelatin in which the calcium content is reduced as much as possible.
  • Calcium of 16 mg/m 2 or more is usually present in the light-sensitive material, unless gelatin from which calcium is especially removed is used.
  • an ion exchange resin and a dialysis treatment are used for removing calcium contained in gelatin.
  • the pyrroloazole-type cyan dye-forming coupler represented by Formula (Ia) is represented by Formulas (IIa) to (VIIIa):
  • R 1 , R 2 and R 3 each are the electron attractive groups having the Hammett's substituent constant ⁇ p value of 0.20 or more, and the total of the ⁇ p values of R 1 and R 2 of 0.65 or more.
  • the total of the ⁇ p values of R 1 and R 2 is preferably 0.70 or more and the upper limit thereof is not more than 1.8.
  • R 1 , R 2 and R 3 each are the electron attractive group having the ⁇ p value of 0.20 or more, preferably 0.35 or more, and more preferably 0.60 or more.
  • the upper limit thereof is 1.0 or less.
  • the Hammett's rule is the rule of thumb which was proposed by L.P. Hammett in 1935 in order to quantitatively discuss the affects exerted to a reaction or equilibrium of a benzene derivative by a substituent. In these days, the propriety thereof is widely accepted.
  • ⁇ p value and ⁇ m value are available as the substituent constant obtained according to the Hammett's rule and the values thereof are described in many general publications. They are described in, for example, "Lange's Handbook of Chemistry” vol. 12, edited by J.A. Dean, 1979 (McGraw-Hill) and "Chemical Region, Extra Edition” No. 122, pp. 96 to 103, 1979 (Nankohdo).
  • R 1 , R 2 and R 3 are regulated by Hammett's substituent constant ⁇ p value but this does not mean that they are limited to the substituents the ⁇ p values of which are described in these publications. Even if the ⁇ p values of the groups would not be described in the publications, they are naturally included in the scope of the present invention as long as they are included in the above range when they are measured according to the Hammett's rule.
  • R 1 , R 2 and R 3 which are the electron attractive groups having the ⁇ p values of 0.20 or more, an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, a diarylphosphinyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, an acylthio group, a sulfamoyl group, a thiocyanate group, a thiocarbonyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated aryl
  • an acyl group for example, acetyl, 3-phenylpropanoyl, benzoyl, and 4-dodecyloxybenzoyl
  • an acyloxy group for example, acetoxy
  • a carbamoyl group for example, carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-(4-n-pentadecanamide)-phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, and N-[3-(2,4-di-t-amylphenoxy)propyl]carbamo
  • the representative ⁇ p values of the electron attractive groups are a cyano group (0.66), a nitro group (0.78), a trifluoromethyl group (0.54), an acetyl group (0.50), a trifluoromethanesulfonyl group (0.92), a methanesulfonyl group (0.72), a benzenesulfonyl group (0.70), a methanesulfinyl group (0.49), a carbamoyl group (0.36), a methoxycarbonyl group (0.45), a pyrazolyl group (0.37), a methanesulfonyloxy group (0.36), a dimethoxyphospholyl group (0.60), and a sulfamoyl group (0.57).
  • an acyl group an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a halogenated alkyl group, a halogenated alkoxy group, a halogenated alkylthio group, a halogenated aryloxy group, a halogenated aryl group, an aryl group substituted with two or more nitro groups, and a heterocyclic group.
  • an acyl group an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group, and a halogenated alkyl group. More preferred are a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a halogenated alkyl group.
  • R 1 and R 2 are preferably that R 1 is a cyano group and R 2 is any of a trifluoromethyl group, a straight-chain or branched unsubstituted alkoxycarbonyl group, an alkoxycarbonyl group substituted with a carbamoyl group, an alkoxycarbonyl group having an ether bond, and an aryloxycarbonyl group that is either unsubstituted or substituted with an alkyl group or an alkoxy group.
  • R 4 represents a hydrogen atom or a substituent (including an atom) preferably having 1 to 36 carbon atoms, and there can be enumerated as the substituent, a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl, aryl or heterocyclic thio group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an alkylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkenyloxy group, a formyl group, an alkyl, aryl or heterocyclic acyl group, an alkyl, aryl or heterocyclic sulfonyl group, an alkyl,
  • R 4 represents a hydrogen atom, a halogen atom (for example, a chlorine atom and a bromine atom), an aliphatic group (for example, a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group, and to be detailed, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxy)propyl, 3-[4- ⁇ 2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamide ⁇ phenyl]propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, and 3-(2,4-d
  • R 4 there can be preferably enumerated as R 4 , an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an imide group, a sulfinyl group, a phosphonyl group, an acyl group
  • an alkyl group and an aryl group More preferred is the alkyl or aryl group having at least one alkoxy group, sulfonyl group, sulfamoyl group, carbamoyl group, acylamide group, or sulfonamide group as a substituent. Particularly preferred is the alkyl or aryl group having at least one acylamide group or sulfonamide group as a substituent.
  • X represents a hydrogen atom or the group (hereinafter referred to as a splitting group) which is split off when the coupler reacts with the oxidation product of an organic primary amine color developing agent.
  • the splitting group is a halogen atom, an aromatic azo group, an alkyl, aryl or heterocyclic group, alkyl- or arylsulfonyl group, arylsulfinyl group, alkoxy, aryloxy or heterocyclic oxy carbonyl group, aminocarbonyl group, or alkyl, aryl or heterocyclic carbonyl group, each bonded to a coupling site via an oxygen, nitrogen, sulfur or carbon atom, or a heterocyclic group bonded to the coupling site via a nitrogen atom in the heterocycle.
  • a halogen atom an alkoxy group, an aryloxy group, an acyloxy group, an alkyl- or arylsulfonyloxy group, an acylamino group, an alkyl- or arylsulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl, aryl or heterocyclic thio group, a carbamoylamino group, an arylsulfinyl group, an arylsulfonyl group, a 5-membered or 6-membered nitrogen-containing heterocyclic group, an imide group, and an arylazo group.
  • the alkyl group, aryl group or heterocyclic group contained in these splitting groups may further be substituted with the substitutents enumerated for R 4 .
  • substituents When these substituents are two or more, they may be the same or different.
  • These groups may further have the substituents enumerated for R 4 .
  • the group represented by X preferably has 1 to 12 carbon atoms.
  • the splitting group is a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom), an alkoxy group (for example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, and ethoxycarbonylmethoxy), an aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, and 2-carboxyphenoxy), an acyloxy group (for example, acetoxy, tetradecanoyloxy, and benzolyoxy), an alkyl- or arylsulfonyloxy group (for example, methanesulfonyloxy and toluenesulfonyloxy), an acylamino
  • These groups may further be naturally substituted with the substitutents enumerated for R 4 .
  • the splitting group may contain the photographically useful groups such as a development inhibitor and a development accelerator.
  • X is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkyl- or arylthio group, an arylsulfonyl group, an arylsulfinyl group, or a 5-membered or 6-membered nitrogen-containing heterocyclic group bonded to a coupling active site via the nitrogen atom.
  • X is more preferably an arylthio group.
  • the group represented by R 1 , R 2 , R 3 , R 4 or X may contain the cyan coupler residue represented by Formula (Ia) to form a dimer or a higher polymer, or the group represented by R 1 , R 2 , R 3 , R 4 or X may bond to a high molecular chain to form a homopolymer or a copolymer.
  • the homopolymer or copolymer containing the high molecular chain is an addition polymer having the cyan coupler residue represented by Formula (Ia), and the typical example thereof is a homopolymer or copolymer of an ethylene type unsaturated compound.
  • one or more kinds of a cyan color development repetitive unit having the cyan coupler residue represented by Formula (Ia) may be contained in the polymer and one or more kinds of a non-color developable ethylene type monomer such as acrylic acid ester, methacrylic acid ester, and maleic acid ester, which is not subjected to a coupling with the oxidation product of an aromatic primary amine developing agent, may be contained in the polymer as a copolymerization component.
  • a non-color developable ethylene type monomer such as acrylic acid ester, methacrylic acid ester, and maleic acid ester, which is not subjected to a coupling with the oxidation product of an aromatic primary amine developing agent
  • the compound and intermediate product thereof can be synthesized by the publicly known methods. They can be synthesized according to the methods described in, for example, J. Am. Chem. Soc. , No. 80, 5332 (1958), J. Am. Chem. Soc. , No. 81, 2452 (1959), J. Am. Chem. Soc. , No. 112, 2465 (1990), Org. Synth. , I, 270 (1941), J. Chem. Soc. , 5149 (1962), Heterocycles , No. 27, 2301 (1988), and Rec. Trav. Chim. , 80, 1075 (1961), the publications cited therein, or the methods equivalent thereto.
  • Synthetic example 1 synthesis of the exemplified compound (9)
  • the exemplified compound (9) was synthesized via the following route:
  • the powder of potassium hydroxide (252 g, 4.5 mole) was added to the dimethylformamide (200 ml) solution of the compound (3a) (101.1 g, 0.3 mole) at room temperature and stirred well. While cooling with water, hydroxylamine-o-sulfonic acid (237 g, 2.1 mole) was added dropwise, taking care that the temperature did not suddenly rise, and after completing the addition, the solution was stirred for 30 minutes. A 0.1 N hydrochloric acid aqueous solution was added dropwise to neutralize the solution which was tested with a pH test paper. The solution was extracted with ethyl acetate three times.
  • the compound (5a) thus obtained 1.8 g and the compound (6a) 12.4 g were dissolved in sulfolane 2.0 ml and further titanium isopropoxide 1.5 g was added thereto.
  • the reaction was carried out for 1.5 hours while maintaining the reaction temperature at 110°C and then ethyl acetate was added, followed by washing with water. After the ethyl acetate phase was dried, the solvent was distilled off and the residue was refined by column chromatography, whereby the desired exemplified compound (9) 1.6 g was obtained.
  • the melting point thereof was 97 to 98C.
  • the cyan coupler When the cyan coupler is applied to a silver halide color light-sensitive material, it may have at least one layer each containing coupler on a support.
  • the layer containing the coupler may be a hydrophilic layer provided on the support.
  • the color light-sensitive material can be of the constitution in which a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated, in this order, on a support, but the order may be different from this. Further, at least one of the above light-sensitive emulsion layers can be replaced with an infrared-sensitive silver halide emulsion layer.
  • the silver halide emulsions having sensitivities in the respective wavelength regions and the couplers forming the dyes having the relationship of a complementary color with the rays to which the emulsions are sensitive can be contained in these light-sensitive emulsions to carry out a color reproduction by a subtractive color process. Also, there may be used a constitution in which the light-sensitive emulsion layers have no such relationship as mentioned above, with the hues of the dyes formed by the couplers.
  • the coupler When the coupler is applied to the light-sensitive material, it is used particularly preferably for a red-sensitive silver halide emulsion layer.
  • the addition amount of the coupler to a light-sensitive material is usually 1 ⁇ 10 -3 to 1 mole, preferably 2 ⁇ 10 -3 to 5 ⁇ 10 -1 mole per mole of silver halide.
  • the preferred coating amount of the cyan coupler is 2.0 ⁇ 10 -6 to 2.0 ⁇ 10 -3 mole, further preferably 2.0 ⁇ 10 -5 to 1.0 ⁇ 10 -3 mole per m 2 of the light-sensitive material.
  • the cyan coupler can be used by arbitrarily mixing the inventive cyan coupler with other known couplers, but the use proportion of the cyan coupler is preferably 5 mole% or more, further preferably 30 mole% or more.
  • Silver halide grains which are contained in the light-sensitive emulsion layer together with the pyrroloazole-type cyan couplers are (a) silver bromochloride grains having a silver chloride content of 90 mole% or more or silver chloride grains, each being chemically sensitized with a gold compound (hereafter "the first embodiment") or (b) silver bromochloride grains containing silver iodide in an amount of 1,0 mole% or less and having a silver chloride content of 90 mole% or more and a silver bromide-rich phase on the grain surface or in the inside thereof having a silver bromide content larger by 5 mole% or more than those at the other portions (hereafter "the second embodiment").
  • the silver chloride content is required to be 90 mole% or more. Further, it comprises preferably silver bromochloride in which 95 mole% or more of the silver halides constituting the silver halide grains is composed of silver chloride and which contains silver iodide in an amount of 1,0 mole% or less, or silver chloride.
  • the more preferred halogen composition of the silver halide grains is of silver bromochloride in which 98 mole% or more of the silver halides constituting the silver halide grains is composed of silver chloride and which contains silver iodide in amount of 1,0 mole% or less, or silver chloride.
  • the silver bromochloride content of the total silver halides constituting the grain which is reduced to less than 90 mole%, is not preferred since the developing speed gets slow. Meanwhile, sufficient sensitivity can not be obtained with pure silver chloride containing no silver bromide at all and therefore it is not preferred as well.
  • the silver halide grains ot the first embodiment preferably have a localization phase having the silver bromide content exceeding at least 10 mole%.
  • Such localization phase (hereinafter referred to as a silver bromide-localized phase) having the silver bromide content higher than that of a substrate is desired to be present in the vicinity of the grain surface in order to demonstrate marked effects of the present invention and further, from the viewpoints of a pressure performance and a processing solution composition dependency.
  • the term "vicinity of the grain surface" used therein means the area present within 1/5 of the grain size of the silver halide grain used, which is measured from the outermost surface thereof. It is present preferably within 1/10 of the grain size of the silver halide grain used, which is measured from the outermost surface thereof.
  • the localization phase having the silver bromide content exceeding at least 10 mole% is epitaxially grown at the corner site of the cubic or tetradecahedral silver chloride grain.
  • the silver bromide content in such the silver bromide-localized phase preferably exceeds 10 mole%, but too high a silver bromide content sometimes provides characteristics unfavorable for the photographic light-sensitive material, such that a desensitization is caused when a pressure is exerted to the light-sensitive material. Sensitivity and a gradation may be changed to a large extent due to changes in the composition of processing solutions. Taking these matters into consideration, the silver bromide content in the silver bromide-localized phase resides preferably in the range of 10 to 60 mole%, more preferably 20 to 50 mole%.
  • the silver bromide-localized phase consists preferably of 0.1 to 20%, more preferably 0.5 to 7% of silver, based on the silver amount constituting the silver halide grains and coexisting with the cyan coupler.
  • the interface between the silver bromide-localized phase and the other phases in the grain may have a distinct phase boundary or a transit area in which the halogen composition gradually changes.
  • Such the silver bromide-localized phase can be formed with various methods. For example, a soluble silver salt and a soluble halide can be reacted by a single mixing method or a simultaneous mixing method to form the localization phase. Further, the localization phase can be formed with a conversion method in which the silver halide grains already formed are converted to silver halide grains having a lower solubility product.
  • the silver bromide-localized phase can be formed by, for example, adding a water-soluble bromide aqueous solution to the cubic or tetradecahedral silver halide host grains, or mixing the above silver halide host grains with the silver bromochloride or silver bromide fine grains having a smaller average grain size and higher silver bromide content than those of the silver halide host grains and then ripening it.
  • the silver bromide-localized phase is formed preferably under the presence of an iridium compound.
  • the silver bromide-localized phase is formed under the presence of the iridium compound" described herein means to supply the iridium compound simultaneously with, immediately before or immediately after the supply of silver or halide for forming the localization phase.
  • the silver bromide-localized phase is formed by adding a water-soluble bromide aqueous solution
  • the iridium compound is preferably added to the aqueous solution in advance, or another solution containing the iridium compound is preferably added at the same time.
  • the iridium compound is preferably incorporated in advance into the silver halide fine grains having the higher silver bromide content.
  • the iridium compound may be allowed to be present in forming the phases other than the silver bromide-localized phase, wherein the silver bromide-localized phase is preferably formed together with at least 50%, more preferably at least 80% of the whole amount of the iridium compound added.
  • the size of the silver halide grains is arbitrary as long as it falls within the conventional range. Preferred is the case that the average grain size thereof is 0.1 to 1.5 ⁇ m.
  • the grain size distribution thereof may be of a monodispersion or polydispersion, and the monodispersion is preferred. In a grain size distribution representing the degree of the monodispersion, the ratio (s/d) of a statistical standard deviation (s) to an average grain size (d) is preferably 0.2 or less, more preferably 0.15 or less. Two or more kinds of the monodispersed emulsions are preferably mixed and used.
  • the silver halide emulsion containing the cyan coupler is required to be chemically sensitized with a gold compound.
  • the gold compound to be used may be of a gold oxidation number of 1 or 3 and various gold compounds can be used.
  • the addition amount of these gold compounds is generally in the range of 1 ⁇ 10 -8 to 1 ⁇ 10 -2 mole, preferably 1 ⁇ 10 -7 to 1 ⁇ 10 -3 mole, and more preferably 1 ⁇ 10 -6 to 1 ⁇ 10 -4 mole per mole of silver halide.
  • gold compounds are added in the preparation of a silver halide emulsion, preferably until finishing a chemical sensitization.
  • At least one of the mercapto compounds shown in JP-A-3-233448 can be added to the silver halide emulsion used in the first embodiment to prevent the increase in a fog, particularly the increase in the fog in using a gold sensitizer to a markedly large extent.
  • they may be added at a grain forming step, a desalting step, or a chemical ripening step, or immediately before coating. They are added preferably at the grain forming step, desalting step or chemical ripening step, particularly before adding the gold sensitizer.
  • the addition amount of the mercapto compounds is preferably 1 ⁇ 10 -6 to 5 ⁇ 10 -2 mole, more preferably 1 ⁇ 10 -4 to 1 ⁇ 10 -2 mole per mole of silver halide.
  • An addition portion is not specifically limited and may be either in a light-sensitive layer or a non-light-sensitive layer.
  • an adding method is not specifically limited as well and may be during either of a silver halide grain formation, a physical ripening, a chemical ripening, and the preparation of a coating solution.
  • the silver halide grains contained in the light-sensitive silver halide emulsion layer containing the cyan dye-forming coupler consist of the silver bromochloride grains containing silver iodide in an amount of 1,0 mole% or less and having the silver chloride content of 90 mole% or more, preferably 95 to 99.9 mole%.
  • the silver bromochloride content of the total silver halides constituting the grain, which is reduced to less than 90 mole%, is not preferred since the developing speed gets slow. Meanwhile, sufficient sensitivity cannot be obtained with pure silver chloride containing no silver bromide at all and therefore it is not preferred in the second embodiment.
  • the grains preferably contain no silver iodid.
  • the values of the above halogen compositions show the average values.
  • the "average value" is the value obtained by averaging the values of the halogen compositions of the whole grains contained in one kind of the silver halide emulstion used in the present invention.
  • the silver halide emulsion contained in this cyan color developing layer contains 50% or more, more preferably 70% or more and most preferably 90% or more by weight of the high silver chloride grains provided with the silver bromide-rich phase as described above.
  • the method in which a water soluble halide solution is added dividing into several times while changing the halogen composition in the water soluble halide solution the method in which a bromide ion-supplying compound is added during or after the grain formation to carry out a halogen conversion, and further the method in which the high silver bromide fine grains are added to precipitate a silver bromide-rich phase on the grains.
  • the provision of the silver bromide-rich phase by a halogen conversion or the addition of the high silver bromide fine grains is carried out preferably before a chemical sensitization process.
  • Group VIII metals and/or the complex ions of the other polyvalent metal ions such as IrCl 6 are preferably contained in the silver bromide-rich phase according to the second embodiment.
  • the degree of the difference between the silver bromide contents of the substrate (the parts other than the silver bromide-rich phase in the silver halide grain) and the silver bromide-rich phase is determined by the mole ratio used of a silver bromide fine grain and a scarcely soluble bromide to a host silver halide grain, the speed of supplying a water soluble bromide to the host silver halide emulsion, and pAg and pH of the reaction solution.
  • the silver bromide-rich phase is formed, for example, by adding a silver nitrate solution and a halogen ion to the host silver halide emulsion at a prescribed speed while controlling pAg and pH. Further, it can be formed as well by adding the scarcely soluble bromide such as a silver bromide fine grain and a silver bromochloride fine grain to carry out a physical ripening, or it can also be formed by substituting the host silver bromochloride with a bromine ion.
  • the uneven and discontinuous or isolated silver bromide-rich phase in the second embodiment is formed preferably by adding a water soluble bromide and a water soluble silver nitrate or adding the silver bromide fine grains to carry out the physical ripening using the so-called CR-compounds described in, for example, JP-A-61-311131, JP-A-62-86252, JP-A-62-86163, JP-A-62-86165, JP-A-62-70005, and JP-A-62-152330.
  • the silver bromide-rich phase has a silver bromide content higher by 5 mole% or more than those in the silver halides adjacent thereto.
  • the silver bromide content in the silver bromide-rich phase preferably exceeds 10 mole%.
  • a too-high silver bromide content sometimes causes unfavorable characteristics such as desensitization when a pressure is applied to the light-sensitive material.
  • the silver bromide content in the silver bromide-rich phase is preferably in the range of 10 to 60 mole%, most preferably 20 to 50 mole%.
  • the silver bromide-rich phase is preferably composed of 0.1 to 5 mole% silver, more preferably 0.2 to 4 mole% silver based on the total silver constituting the silver halide grains according to the second embodiment.
  • the silver bromide-rich phase containing at least 10 mole% of silver bromide based on the total silver bromide contained in the silver bromide-rich phases is epitaxially grown preferably in the vicinity of a grain peak.
  • the "vicinity of the peak" represents the inside of the square in which one side thereof corresponds to 1/3, more preferably 1/5 of the diameter of the circle having the same area as that of the projected cube or corresponding-to-cube regular crystal silver bromochloride grain and the peak of the grain (the intersecting point of the sides of the regular crystal grain which is cube or assumed to be cube) is one of the corners thereof.
  • a sulfur sensitizer is preferably used during the chemical ripening process.
  • the well-known unstable sulfur compounds such as thiosulfate (for example, hypo), thioureas (for example, diphenyl thiourea, triethyl thiourea and allyl thiourea), and rhodanines. They can be used in the amount of 10 -7 to 10 -2 mole per mole of silver halide.
  • Noble metal sensitizers such as gold, platinum, palladium, and iridium are also preferably used in combination or singly.
  • a gold sensitizer is used preferably in combination with the sulfur sensitizer.
  • chlorauric acid potassium chloraurate, potassium aurithiocyanate, gold sulfide, and gold selenide. They can be used in the amount of 10 -7 to 10 -2 mole per mole of silver halide.
  • a selenium sensitizer and a tellurium sensitizer are preferably used as well in combination.
  • JP-B-44-15748 the term "JP-B" as used herein means an examined Japanese patent publication
  • the compounds such as colloidal selenium, selenoureas (for example, N,N-dimethyl selenourea, selenourea and tetramethyl selenourea), selenoamides (for example, selenoacetoamide and N,N-dimethylselenobenzamide), selenoketones (for example, selenoacetone and selenobenzophenone), selenides (for example, triphenyl phosphine selenide and diethyl selenide), selenophosphates (for example, tri-p-tolylselenophosphate), selenocarboxylic acids and esters thereof, and isoselenocyanates. They can be used in the amount of 10 -8 to 10 -3 mole per mole of silver halide.
  • a reduction sensitizer is preferably used as well.
  • stannous chloride aminoiminomethanesulfinic acid, a hydrazine derivative, a borane compound (for example, diethylamine borane), a silane compound, and a polyamine compound.
  • the chemical sensitization is preferably carried out as well in the presence of a silver halide solvent.
  • thiocyanate for example, potassium thiocyanate
  • a thioether compound the compounds described in, for example, U.S. Patents 3,021,215 and 3,271,157, JP-B-58-30571, and JP-A-60-136736, in particular, for example, 3,6-dithia-1,8-octanediol
  • a tetra-substituted thiourea compound described in, for example, JP-B-59-11892, and U.S.
  • particularly thiocyanate are particularly thiocyanate, the thioether compounds, the tetra-substituted thiourea compounds, and the thione compounds. They can be used in the amount of 10 -5 to 10 -2 mole per mole of silver halide.
  • the silver halide grains according to the second embodiment may have a (100) face, a (111) face, or both of the faces, or may contain a higher order face. Cube or tetradecahedron consisting primarily of the (100) face is preferred.
  • the size of the silver halide grains is arbitrary as long as it falls within the range usually used. Preferred is the case that the average grain size thereof is 0.1 to 1.5 mm.
  • the grain size distribution thereof may be of a mono-dispersion or polydispersion, and the monodispersion is preferred.
  • the ratio (s/d) of a satistical standard deviation (s) to an average grain size (d) is preferably 0.2 or less, more preferably 0.15 or less.
  • two or more kinds of the above monodispersed emulsions are preferably mixed and used for the same layer, or simultaneously coated.
  • the emulsion used in the second embodiment can be synthesized by the methods described in Chemie et Phisique Photographique written by P. Glafkides (published by Paul Montel Co., Ltd., 1967), Photographic Emulsion Chemistry written by G.F. Duffin (published by Focal Press Co., Ltd., 1966), and Making and Coating Photographic Emulsion written by V.L. Zelikman, (published by Focal Press Co., Ltd., 1964).
  • any of an acid method, a neutral method and an ammonia method there may be used any of an acid method, a neutral method and an ammonia method.
  • Any of a single jet method, a double jet method and the combination thereof may be used as the method for allowing a water soluble silver salt to react with a water soluble halide.
  • a so-called reverse mixing method There can be used as one form of the double jet method, the method in which pAg of the solution in which the sliver halide grains are formed is maintained constant, that is, a so-called controlled double jet method. With this method a silver halide emulsion having a regular crystal form and an almost uniform grain size can be obtained.
  • Various polyvalent metal ion impurities can be introduced into the silver halide emulsion of the second embodiment for the purposes of improving a sensitivity, a temperature and humidity dependency in exposing, and a latent image preservability in the course of an emulsion grain formation and a physical ripening.
  • the salts of cadmium, zinc, lead, copper, and thallium, and the salts or complex salts of iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum which are the elements of the Group VIII.
  • the above Group VIII elements can be preferably used.
  • the addition amount of these compounds is over a broad range according to the desired purpose and is preferably 10 -9 to 10 -2 mole per mole of silver halide.
  • the spectral sensitization is carried out for the purpose of providing the emulsions contained in the respective layers of the light-sensitive material of the present invention with the spectral sensitivities in the prescribed wavelength regions.
  • a dye absorbing rays in the wavelength region corresponding to the desired spectral sensitivity-spectral sensitizing dye can be given as the spectral sensitizing dye used for the above purpose, the compounds described in, for example, Heterocyclic Compounds-Cyanine Dyes and Related Compounds written by F.M. Harmer (published by John Wiley & Sons, New York, London, 1964).
  • Those described at the right upper column of the page 22 to the page 38 of JP-A-62-215272 are preferably used as the specific examples of the compound and the spectral sensitizing method.
  • the emulsion used in the present invention may be either a so-called surface latent image-type emulsion in which a latent image is formed mainly on a grain surface or a so-called inner latent image type emulsion in which the latent image is formed mainly in the inside of the grain.
  • the content of calcium atoms contained in the photographic constitutional layer consisting of the silver halide emulsion layers and non-light-sensitive hydrophilic layers (a protective layer, an intermediate layer and a subbing layer) is reduced to 15 mg/m 2 or less to allow the effects of the present invention to be more markedly demonstrated.
  • the calcium content is more preferably 1 to 10 mg/m 2 , most preferably 2 to 8 mg/m 2 .
  • the calcium content (the amount converted to a calcium atom, the same will be applied hereinafter) depends primarily on the calcium content in the gelatin used as a binder in a silver halide photographic light-sensitive material. In particular, if gelatin which is not subjected to a treatment for removing calcium is used, 16 mg/m 2 or more of calcium will usually be contained in the silver halide light-sensitive material.
  • any gelatin may be used as long as the calcium content thereof is 15 mg/m 2 or less.
  • the silver halide light-sensitive material prepared by using partially or entirely gelatin with the reduced calcium content, which is obtained by subjecting gelatin once or several times to processing with an ion exchange resin or a dialysis processing.
  • a hydrophilic colloid layer of the light-sensitive material for the purpose of improving the sharpness of an image, there are preferably incorporated into a hydrophilic colloid layer of the light-sensitive material according to the present invention so that the optical reflection density of the light-sensitive material in 680 nm becomes 0.70 or more, the dyes (among them, an oxonol series dye) capable of being decolored by processing, described at pages 27 to 76 of European Patent EP 0,337,490A2, and into an anti-water resin layer of a support, titanium oxide which is subjected to a surface treatment with di- to tetrahydric alcohols (for example, trimethylolethane) in the proportion of 12% by weight or more (more preferably 14% by weight or more).
  • di- to tetrahydric alcohols for example, trimethylolethane
  • organic high boiling solvent for the photographic additives capable of being used in the present invention, such as the cyan, magenta and yellow couplers
  • any ones can be used as long as they are the compounds which have a melting point of 100°C or less and a boiling point of 140°C or more and which are immiscible with water and are the good solvents for the couplers.
  • the organic high boiling solvent has preferably a melting point of 80°C or less. It has preferably a boiling point of 160°C or more, more preferably 170°C or more.
  • the cyan, magenta and yellow couplers can be impregnated in a loadable latex polymer (for example, U.S. Patent 4,203,716) or dissolved together with a water insoluble and organic solvent soluble polymer under the presence or absence of the above organic high boiling solvent to be emulsified and dispersed in a hydrophilic colloid aqueous solution.
  • a loadable latex polymer for example, U.S. Patent 4,203,716
  • a water insoluble and organic solvent soluble polymer under the presence or absence of the above organic high boiling solvent to be emulsified and dispersed in a hydrophilic colloid aqueous solution.
  • the color image preservability-improving compounds described in European Patent EP 0,277,589A2 are preferably used together with a coupler.
  • they are used preferably in combination with a pyrazoloazole coupler and a pyrroloazole coupler.
  • the compounds (F) which are chemically combined with an aromatic amine type developing agent remaining after a color development processing to form a chemically inactive and substantially colorless compound and/or the compounds (G) which are chemically combined with the oxidation product of an aromatic amine type developing agent remaining after a color development processing to form a chemically inactive and substantially colorless compound.
  • anti-mold agents described in JP-A-63-271247 are preferably added to the light-sensitive material according to the present invention for the purpose of preventing various molds and bacteria which grow in a hydrophilic colloid layer to deteriorate an image.
  • a support used for the light-sensitive material, for display a white color polyester series support or a support in which a layer containing a white pigment is provided on a support side having a silver halide emulsion layer.
  • An anti-halation layer is preferably provided on a support side coated thereon with a silver halide emulsion layer or the backside thereof in order to further improve a sharpness.
  • the transmission density of a support is controlled preferably in the range of 0.35 to 0.8 so that a display can be admired with either a reflected light or a transmitted light.
  • the light-sensitive material according to the present invention may be exposed with either a visible ray or an infrared ray.
  • An exposing manner may be either a low illuminance exposure or a high illuminance and short time exposure.
  • Particularly preferred for the present invention is an exposing system in which an exposing time per a picture element is shorter than 10 -3 second and more preferred is a laser scanning exposing system in which an exposing time per a picture element is shorter than 10 -4 second.
  • An exposed light-sensitive material can be subjected to a conventional color development processing and for the purpose of a rapid processing, it is preferably subjected to a bleach-fixing processing after the color development.
  • pH of the bleach-fixing solution is preferably 6.5 or less, more preferably about 6 or less for the purpose of accelerating desilver.
  • the method described in a left upper column at page 27 to a right upper column at page 34 of JP-A-2-207250 can be preferably applied as the method for processing a silver halide color light-sensitive material in which a high silver chloride emulsion having a silver chloride content of 90 mole% or more is used.
  • a solution prepared by dissolving silver nitrate 80 g in distilled water 300 ml and a solution prepared by adding sodium chloride 24.3 g and potassium hexacyanoferrate (III) trihydrate 4 mg in distilled water 300 ml were added and mixed over the period of 20 minutes while maintaining the temperature at 53°C.
  • the emulsion was subjected to a desalting and a rinsing at 40°C.
  • lime-treated gelatin 90 g was added and further pAg and pH were adjusted to 7.4 and 6.4, respectively, with sodium chloride and sodium hydroxide.
  • Emulsion R 1 The silver bromochloride emulsion thus obtained was designated as Emulsion R 1 .
  • Emulsion R 3 was prepared in the same manner as that in Emulsion R 1 except that the sulfur sensitization with triethyl thiourea was replaced with a gold sensitization with chlorauric acid of 2 ⁇ 10 -5 mole per mole of silver halide.
  • the coating solutions were prepared in the following manner.
  • the coating solutions for the first layer to seventh layer were prepared in the same manner as that in the fifth layer coating solution.
  • Sodium 1-oxy-3,5-dichloro-s-triazine was used as the hardener for the respective layers.
  • Cpd-15 and Cpd-16 were added to the respective layers so that the whole amounts thereof became 25.0 mg/m 2 and 50.0 mg/m 2 , respectively.
  • 4-hydroxy-6-methyl-1,3,3a,7-tetra-azaindene was added to the blue-sensitive emulsion layer and green-sensitive emulsion layer in the amounts of 1 ⁇ 10 -4 mole and 2 ⁇ 10 -4 mole per mole of silver halide, respectively.
  • the following dye (the numeral in the paren-thesis represents a coated amount) was added to the emulsion layers to prevent an irradiation:
  • Silver bromochloride emulsion (cube, 5:5 mixture (Ag mole ratio) of the large size emulsion B1 having the average grain size of 0.80 ⁇ m and the small size emulsion B2 having the average grain size of 0.65 ⁇ m, wherein the fluctuation coefficients in the grain size distributions were 0.08 and 0.09, respectively, and either size emulsions comprised the grains in which silver bromide 0.4 mol% was localized on a part of the grain surface and the rest was silver chloride) 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Dye image stabilizer (Cpd-1) 0.08 Dye image stabilizer (Cpd-2) 0.04 Dye image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13
  • Second layer (an anti-color mixing layer):
  • Silver bromochloride emulsion (cube, 6:4 mixture (Ag mole ratio) of the large size emulsion G1 having the average grain size of 0.55 ⁇ m and the small size emulsion G2 having the average grain size of 0.39 ⁇ m, wherein the fluctuation coefficients in the grain size distributions were 0.10 and 0.08, respectively, and either size emulsions comprised the grains in which silver bromide 0.8 mol% was localized on a part of the grain surface and the rest was silver chloride) 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Dye image stabilizer (Cpd-6) 0.15 Dye image stabilizer (Cpd-2) 0.03 Dye image stabilizer (Cpd-7) 0.01 Dye image stabilizer (Cpd-8) 0.01 Dye image stabilizer (Cpd-9) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15
  • Average molecular weight about 60,000
  • UV absorber (UV-1) UV absorber
  • gelatin contained in the respective layers was added so that the ratio thereof to an oil soluble component was kept fixed.
  • the light-sensitive materials were prepared in the same manner as above except that the emulsion and cyan coupler contained in the red-sensitive emulsion layer were replaced as shown in Table 1. These samples were designated as Samples 101 to 118, provided that the coated amounts of the emulsion and cyan coupler in the fifth layer (the red-sensitive emulsion layer) in the samples in which the cyan couplers (10) and (11) were used were set at 0.17 g/m 2 and 0.16 g/m 2 , respectively.
  • the coated amounts of the emulsion and cyan coupler in the fifth layer (the red-sensitive emulsion layer) in the samples in which the cyan coupler (20) was used were set at 0.12 g/m 2 and 0.16 g/m 2 , respectively.
  • Samples 113 to 115 were prepared in the same manner as that in Samples 107 to 109 except that the yellow coupler (ExY) contained in the first layers (the blue-sensitive emulsion layer) in Samples 107 to 109 was replaced with the same mole of the yellow coupler (ExY-2) and that the coated amount including that of the coupler in the first layer was reduced to 80% by weight without changing the composition thereof.
  • the yellow coupler (ExY) contained in the first layers (the blue-sensitive emulsion layer) in Samples 107 to 109 was replaced with the same mole of the yellow coupler (ExY-2) and that the coated amount including that of the coupler in the first layer was reduced to 80% by weight without changing the composition thereof.
  • Samples 116 to 118 were prepared in the same manner as that in Samples 110 to 112 except that the yellow coupler contained in the first layer in Samples 110 to 112 was replaced with the same mole of the yellow coupler (ExY-3) and that the coated amount including that of the coupler in the first layer was reduced to 70% by weight without changing the composition thereof.
  • the prescribed amount of the bleach-fixing solution was separately added to the developing solution. Processing step Temperature Time Color developing 35°C 45 seconds Bleach-fixing 30 to 35°C 45 seconds Rinsing I 30 to 35°C 20 seconds Rinsing J 30 to 35°C 20 seconds Rinsing K 30 to 35°C 20 seconds Drying 70 to 80°C 60 seconds
  • compositions of the respective processing solutions are as follows: Color developing solution Amount Water 800 ml Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-N-( ⁇ -methanesulfonamidethyl)-3-methyl-4-aminoaniline 5.0 g sulfate N,N-bis(carboxymethyl) hydrazine 4.0 g Monosodium N,N-di(sulfoethyl) hydroxylamine 4.0 g Fluorescent whitening agent (Whitex 4B manufactured by Sumitomo Chem.
  • Deionized water (contents of calcium and magnesium: each 3 ppm or less)
  • the degrees of the mixing of the bleach-fixing solution into the developing solution were set at 0 ml/l, 0.2 ml/l and 0.4 ml/l.
  • the processed samples thus prepared were subjected to the measurement of a reflection density to obtain a characteristic curve.
  • the sensitivity was defined by the reciprocal of the exposure necessary to give the density higher by 0.5 than a fog density and expressed by the value relative to the sensitivity of Sample 101 at the exposure of 1 second (the degree of the mixing of the bleach-fixing solution into the developing solution: 0 ml/l), which was set at 100.
  • the sensitivities at the mixing degrees of 0 ml/l, 0.2 ml/l and 0.4 ml/l were designated as Sa, Sb and Sc.
  • the gradation was defined by the difference between the exposure corresponding to the density higher by 0.5 than that that corresponding to a sensitivity and the exposure corresponding to the sensitivity.
  • the gradations at the mixing degrees of 0 ml/l, 0.2 ml/l and 0.4 ml/l were designated as ⁇ a, ⁇ b and ⁇ c.
  • the compatibility of the excellent color reproduction with the reduced change in the photographic performances against the mixing degrees of the bleach-fixing solution into the developing solution could be achieved by the combination of the cyan coupler of the present invention and the emulsion subjected to a gold sensitization. Further, it was newly found that the samples having this combination had less change in photographic performances due to the mixing degrees of the bleach-fixing solution into the developing solution than those in the samples in which ExC was used as the cyan coupler.
  • EXAMPLE 2 Samples 201 to 209 in which the layer constitution in Example 1 was changed as follows were prepared and evaluated in the same manner as that in Example 1, provided that the coated amounts of the emulsion and cyan coupler contained in the fifth layer (the red-sensitive emulsion layer) in the samples in which the cyan couplers (19) and (11) were used were set at 0.17 g/m 2 and 0.16 g/m 2 , respectively.
  • the coating solutions were prepared in the following manner.
  • This solution was emulsified and dispersed in a 10% gelatin aqueous solution with a high speed stirring emulsifier, whereby the emulsified dispersion was prepared.
  • the emulsified dispersion thus obtained and the silver bromochloride emulsion prepared in the manner shown above were mixed and dissolved, whereby the fifth layer coating solution was prepared so that it was of the following composition.
  • the coating solutions for the first layer to seventh layer were prepared in the same manner as that in the fifth layer coating solution. Sodium 1-oxy-3,5-dichloro-s-triazine was used as the hardener for the respective layers.
  • Cpd-15 and Cpd-16 were added to the respective layers so that the whole amounts thereof became 25.0 mg/m 2 and 50.0 mg/m 2 , respectively.
  • the same compounds as those used in Example 1 were used for the silver bromochloride emulsions used in the respective light-sensitive emulsion layers in the same amounts as those used in Example 1 to carry out a spectral sensitization.
  • the same dye as that used in Example 1 was added to the emulsion layers in the same amount for the prevention of an irradiation.
  • compositions of the respective layers are shown below.
  • the numerals represent the coated amounts (g/m 2 ).
  • the coated amounts of the silver halide emulsions are expressed in terms of the amounts converted to silver.
  • First layer (a blue-sensitive yellow color developing layer):
  • Silver bromochloride emulsion (the same as the emulsion in the first layer in Example 1) 0.30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Dye image stabilizer (Cpd-17) 0.19 Solvent (Solv-8) 0.18 Solvent (Solv-1) 0.18 Dye image stabilizer (Cpd-1) 0.06
  • Second layer (an anti-color mixing layer):
  • Third layer (a green-sensitive magenta color developing layer):
  • Silver bromochloride emulsion (the same as the emulsion in the third layer in Example 1 except that this emulsion was the 1:3 mixture (Ag mole ratio) of the large size emulsion G1 and the small size emulsion G2) 0.14 Gelatin 1.28 Magenta coupler (ExM) 0.23 Dye image stabilizer (Cpd-9) 0.03 Dye image stabilizer (Cpd-6) 0.16 Dye image stabilizer (Cpd-18) 0.02 Dye image stabilizer (Cpd-2) 0.02 Solvent (Solv-7) 0.40
  • Seventh layer (a protective layer):
  • Samples 301 to 309 were prepared in the same manner as those in Samples 101 to 109 except that whole gelatins contained in the respective light-sensitive materials were replaced with gelatin ⁇ having a reduced calcium content, as shown in Table 5.
  • the sample x in which the fifth layer (the red-sensitive emulsion layer) coating solution was coated immediately after it was prepared the sample y in which the coating solution was coated after it was stored at 40°C for 2 hours, and the sample z in which the coating solution was coated after it was stored at 40°C for 8 hours were prepared for each of the samples.
  • the red sensitivities Sx, Sy and Sz were obtained in the same manner as that in Example 1 and Sx-Sy ( ⁇ S 1 ) and Sx-Sz ( ⁇ S 2 ) were settled as the standard for the storage stability of the coating solutions.
  • Gelatin ⁇ having less calcium content was prepared by subjecting gelatin used in Example 1 to a lime treatment to remove calcium. There was measured the whole calcium content in the light-sensitive materials of above Samples 301 to 309 prepared by using this gelatin ⁇ to find that it was 6.4 mg/m 2 . Meanwhile, the whole calcium content in the light-sensitive materials in which gelatin subjected to no decalcium treatment was 30.5 mg/m 2 .
  • aqueous solution containing silver nitrate 0.5 mole and an aqueous solution containing sodium chloride 0.4 mole were added to and mixed with a solution prepared by adding sodium chloride 3.3 g to a 3% aqueous solution of lime-treated gelatin at 66°C while vigorously stirring. Subsequently, an aqueous solution containing silver nitrate 0.45 mole and an aqueous solution containing sodium chloride 0.36 mole and potassium bromide 0.09 mole were added and mixed at 66°C while vigorously stirring. Thereafter, the emulsion was subjected to a desalting in which settling and washing with water were carried out 40°C.
  • An emulsion was prepared in the same manner as that in Emulsion R 101 except that the silver nitrate aqueous solution and halide ion aqueous solution each added at the first time were replaced with an aqueous solution containing silver nitrate 0.76 mole and an aqueous solution containing sodium chloride 0.76 mole, respectively and that the silver nitrate aqueous solution and the halide ion aqueous solution each added at the second time were replaced with an aqueous solution containing silver nitrate 0.19 mole and an aqueous solution containing sodium chloride 0.095 mole and potassium bromide 0.095 mole, respectively.
  • the emulsion thus obtained was designated as R 103.
  • an aqueous solution containing silver nitrate 0.019 mole and an aqueous solution containing potassium bromide 0.019 mole were added at 66°C while vigorously stirring, and then the emulsion was subjected to a desalting in which settling and washing with water were carried out at 40°C. Further, lime-treated gelatin 90.0 g was added and pH and pAg of the emulsion were adjusted. Then, triethyl thiourea was added to subject the emulsion to an optimum chemical sensitization so that a surface latent image type emulsion was obtained. The emulsion thus obtained was designated as R 104.
  • aqueous solution containing silver nitrate 0.5 mole and an aqueous solution containing sodium chloride 0.5 mole were added to and mixed with a solution prepared by adding sodium chloride 3.3 g to a 3% aqueous solution of lime-treated gelatin at 66°C while vigorously stirring. Subsequently, an aqueous solution containing silver nitrate 0.431 mole and the aqueous solution containing sodium chloride 0.431 mole were added and mixed at 66°C while vigorously stirring. Thereafter, the emulsion was subjected to a desalting in which settling and washing with water were carried out at 40°C.
  • the lime-treated gelatin 90.0 g was added and pH and pAg of the emulsion were adjusted.
  • the silver bromide fine grain emulsion with the grain size of 0.05 ⁇ m was added to this emulsion at 50°C in the silver amount of 0.019 mole to form a silver bromide-rich phase on the grain surface.
  • the emulsion was subjected to an optimum chemical sensitization with triethyl thiourea.
  • the emulsion thus obtained was designated as R 106.
  • the emulsion was prepared in the same manner as that in Emulsion R 106 except that the halide ion aqueous solution added at the second time was replaced with an aqueous solution containing sodium chloride 0.431 mole and potassium hexacyanoferrate (II) trihydrate 0.003 g and further that potassium hexachloroiridate (IV) 0.2 mg per 0.019 mole of silver was allowed to be contained in the silver bromide fine grains during the emulsion grain formation.
  • the emulsion thus obtained was designated as R 107.
  • the grain size was represented by the average value of the diameters of the circles having the same areas as the projected areas of the grains. The value obtained by dividing the standard deviation of the grain sizes with the average grain size was used to represent the grain size distribution.
  • An X ray diffraction from a silver halide crystal was measured to determine the halogen composition of the emulsion grains.
  • the diffraction angle in the diffraction beam from a (200) face was measured in detail with a monochromatized CuKa beam used as a radiating source. While the diffraction beam from a crystal having a uniform halogen composition gives a single peak, the diffraction beam from a silver halide crystal having a silver bromide-rich phase with a different halogen composition gives the plural diffraction patterns corresponding to the compositions thereof.
  • a lattice constant can be calculated from the diffraction angles in the peaks measured to determine the composition of silver halides constituting the crystal.
  • the coating solutions were prepared in the following manner.
  • the silver bromochloride emulsion B' (cube, the 6:4 mixture (Ag mole ratio) of the large size emulsion with the average grain size of 0.88 ⁇ m and the small size emulsion with the average grain size of 0.70 ⁇ m, wherein the fluctuation coefficients in the grain size distributions were 0.08 and 0.10, respectively, and either size emulsions contained the grains in which silver bromide 0.3 mol% was localized on a part of the grain surface).
  • Cpd-15 and Cpd-16 were added to the respective layers so that the whole amounts thereof became 25.0 mg/m 2 and 50.0 mg/m 2 , respectively.
  • Sensitizing dyes A to E were used for the silver bromochloride emulsions contained in the respective light-sensitive emulsion layers in the same manner as in Example 1.
  • 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to the blue-sensitive layer and green-sensitive layer in the amounts of 1 ⁇ 10 -4 mole and 2 ⁇ 10 -4 mole per mole of silver halide, respectively.
  • compositions of the respective layers are shown below.
  • the numerals represent the coated amounts (g/m 2 ).
  • the coated amounts of the silver halide emulsions are expressed in terms of the amounts converted to silver.
  • Polyethylene laminated paper [polyethylene coated on the 1st layer side contains a white pigment (titanium oxide) and a blue dye (ultramarine)].
  • First layer (a blue-sensitive emulsion layer):
  • Second layer (an anti-color mixing layer):
  • Third layer (a green-sensitive emulsion layer):
  • Silver bromochloride emulsion (cube, 6:4 mixture (Ag mole ratio) of the large size emulsion having the average grain size of 0.55 ⁇ m and the small size emulsion having the average grain size of 0.39 ⁇ m, wherein the fluctuation coefficients in the grain size distributions were 0.10 and 0.08, respectively, and either size emulsions comprised the grains in which silver bromide 0.8 mol% was localized on a part of the grain surface and the rest was silver chloride) 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Dye image stabilizer (Cpd-6) 0.15 Dye image stabilizer (Cpd-2) 0.03 Dye image stabilizer (Cpd-7) 0.01 Dye image stabilizer (Cpd-8) 0.01 Dye image stabilizer (Cpd-9) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15
  • Fourth layer (an anti-color mixing layer):
  • the samples were prepared so that the calcium contents in the light-sensitive materials became 16 mg/m 2 in Samples 401 to 415 and 7 mg/m 2 in Samples 416 to 422, respectively by changing the mixing ratio of gelatin with the calcium content of 3000 ppm and gelatin with the calcium content of 100 ppm.
  • the color development processing was carried out on the following conditions to thereby obtain three kinds of the processed samples:
  • compositions of the respective processing solutions are as follows:
  • the processed samples thus obtained were subjected to the measurement of a reflection density to obtain a so-called characteristic curve.
  • a sensitivity was defined by the reciprocal of the exposure giving the density higher by 0.5 than a fog density and expressed by the value relative to the sensitivity of Sample 101 subjected to the 45 seconds processing in the fresh developing solution, which was set at 100.
  • the gradation was shown by the difference between the logarithmic values of the exposures providing the densities of 1.8 and 2.2, respectively. The smaller this value is, the harder the gradation means to be.
  • Table 8 The results are summarized in Table 8.
  • Samples 410 to 415 each having the constitution of the present invention, there can be obtained the light-sensitive materials capable of rapidly processing with the small softening in processing in the running (equilibrium) developing solution and the high sensitivity. Further, it can be found that the change from the coupler ExC different from the coupler of the present invention to the cyan coupler of the present invention reduces the desensitization stripes generated when the emulsion provided with the silver bromide-rich phase is used (comparison of Sample 403 with Sample 410). Accordingly, the light-sensitive materials capable of rapidly processing and providing less softening and desensitization stripes in the continuous processing can be obtained only by the present invention.
  • Emulsions R 201 to R 207 were prepared in the same manner as that in Example 4 except that the emulsions were subjected to an optimum chemical sensitization with triethyl thiourea and chlorauric acid.
  • the yellow coupler (ExY) contained in the first layer (the blue-sensitive layer) in Samples 401 to 422 in Example 4 was replaced with ExY-2 in the same mole, the coated amount in the first layer including that of the coupler was reduced to 80% without changing the composition thereof, and further the emulsion contained in the fifth layer (the red-sensitive layer) was replaced with the above emulsions R 201 to R 207 as shown in Table 9.
  • These samples were evaluated in the same manner as that in Example 4 and the results thereof are summarized in Table 9. Provided that the 30 seconds processing in the fresh developing solution was omitted.
  • Samples 701 to 712 were prepared and evaluated in the same manners as those in Example 4 except that the layer constitution was changed as follows.
  • compositions of the respective layers are shown below.
  • the numerals represent the coated amounts (g/m 2 ).
  • the coated amounts of the silver halide emulsions are expressed in terms of the amounts converted to silver.
  • First layer (a blue-sensitive emulsion layer):
  • Third layer (a green-sensitive emulsion layer):
  • Silver bromochloride emulsion (cube, 1:3 mixture (Ag mole ratio) of the large size emulsion having the average grain size of 0.55 ⁇ m and the small size emulsion having the average grain size of 0.39 ⁇ m, wherein the fluctuation coefficients in the grain size distributions were 0.10 and 0.08, respectively, and either size emulsions comprised the grains in which silver bromide 0.8 mol% was localized on a part of the surface thereof) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Dye image stabilizer (Cpd-9) 0.03 Dye image stabilizer (Cpd-6) 0.16 Dye image stabilizer (Cpd-18) 0.02 Dye image stabilizer (Cpd-2) 0.02 Solvent (Solv-7) 0.40
  • Fourth layer (a UV absorbing layer):
  • Silver bromochloride emulsion (cube, 1:4 mixture (Ag mole ratio) of the large size emulsion having the average grain size of 0.58 ⁇ m and the small size emulsion having the average grain size of 0.45 ⁇ m, wherein the fluctuation coefficients in the grain size distributions were 0.09 and 0.11, respectively, and either size emulsions comprised the grains in which silver bromide 0.6 mol% was localized on a part of the surface thereof) 0.23 Gelatin 1.04 Cyan coupler (ExC'') 0.32 Dye image stabilizer (Cpd-9) 0.03 Dye image stabilizer (Cpd-18) 0.02 UV absorber (UV-2) 0.18 Dye image stabilizer (Cpd-1) 0.40 Dye image stabilizer (Cpd-20) 0.05 Solvent (Solv-10) 0.14
  • Seventh layer (a protective layer):
  • the effects of the present invention are valid even where the layer constitution is changed as shown above and the light-sensitive materials in which the softening generated when the running (equilibrium) developing solution is used is small and the desensitization stripes are reduced can be obtained only by the constitution of the present invention.

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Claims (13)

  1. Matériau photographique couleur photosensible à halogénure d'argent comprenant un support et des couches constitutives photographiques fournies sur celui-ci comprenant à raison d'au moins une couche chacune, une couche d'émulsion photosensible à halogénure d'argent contenant un agent de couplage formant un pigment jaune, une couche d'émulsion photosensible à halogénure d'argent contenant un agent de couplage formant un pigment magenta, et une couche d'émulsion photosensible à halogénure d'argent contenant un agent de couplage formant un pigment cyan, et au moins une couche non photosensible, dans lequel la couche d'émulsion à halogénure d'argent contenant un agent de couplage formant un pigment cyan contient (i) au moins l'un des agents de couplage cyan pyrroloazole représentés par la formule (Ia), et (ii) des grains d'halogénure d'argent choisis dans le groupe formé par (a) les grains de bromochlorure d'argent ayant une teneur en chlorure d'argent de 90% en moles ou plus, ou les grains de chlorure d'argent, chacun étant sensibilisé chimiquement avec un composé de l'or, et (b) les grains de bromochlorure d'argent contenant de l'iodure d'argent en une quantité de 1,0% en moles ou moins et ayant une teneur en chlorure d'argent de 90% en moles ou plus, et une phase riche en bromure d'argent sur la surface des grains ou à l'intérieur de ceux-ci, ayant une teneur en bromure d'argent supérieure de 5% en moles ou plus à celle de ceux au niveau des autres portions, dans lequel la quantité totale de calcium contenu dans les couches constitutives photographiques précédentes est de 15 mg ou moins par m2 du matériau photosensible :
    Figure 01680001
    dans laquelle Za représente -NH- ou -CH(R3)-, et Zb et Zc représentent chacun -C(R4)= ou -N= ; R1, R2 et R3 représentent chacun un groupe attracteur d'électrons ayant une constante de substituant de Hammett σp de 0,20 ou plus, à condition que la somme des valeurs σp de R1 et R2 soit de 0,65 ou plus ; R4 représente un atome d'hydrogène ou un substituant, à condition que, lorsque deux R4 sont présents dans la formule, ils puissent être identiques ou différents ; X représente un atome d'hydrogène ou un groupe capable de se séparer par clivage lors d'une réaction avec un produit d'oxydation d'un révélateur couleur à base d'amine primaire aromatique ; le groupe représenté par R1, R2, R3, R4 ou X peut devenir un groupe divalent et se combiner pour former un dimère ou un polymère supérieur à un dimère ou se lier à une chaíne de masse moléculaire élevée en formant un homopolymère ou un copolymère.
  2. Matériau photosensible selon la revendication 1, dans lequel lesdits grains à halogénure d'argent sont des grains de bromochlorure d'argent ayant une teneur en chlorure d'argent de 90% en moles ou plus, ou des grains de chlorure d'argent, chacun étant sensibilisé chimiquement avec un composé de l'or.
  3. Matériau photosensible selon la revendication 1 ou 2, dans lequel lesdits grains à halogénure d'argent sont des grains de bromochlorure d'argent ne contenant essentiellement pas d'iodure d'argent et ayant une teneur en chlorure d'argent de 90% en mols ou plus et une phase riche en bromure d'argent sur la surface des grains et à l'intérieur de ceux-ci ayant une teneur en bromure d'argent supérieure de 5% en moles ou plus à celle de ceux au niveau des autres portions.
  4. Matériau photosensible selon l'une quelconque des revendications 1 à 4, dans lequel ledit agent de couplage cyan pyrroloazole est représenté par la formule (IIa), (IIIa) ou (IVa) :
    Figure 01690001
    dans lesquelles R1, R2, R3, R4 et X sont tels que définis dans la formule (Ia).
  5. Matériau photosensible selon l'une quelconque des revendications 1 à 4 dans lequel ledit agent de couplage cyan pyrroloazole est contenu à raison de 1 x 10-3 à 1 mole par mole d'halogénure d'argent.
  6. Matériau photosensible selon la revendication 5, dans lequel la quantité de revêtement dudit agent de couplage cyan pyrroloazole est de 2,0 x 10-6 à 2,0 x 10-3 mole par m2 du matériau photosensible.
  7. Matériau photosensible selon la revendication 2, dans lequel la composition halogénée desdits grains d'halogénure d'argent se compose de chlorure d'argent ou de bromochlorure d'argent contenant 98% en moles ou plus de chlorure d'argent.
  8. Matériau photosensible selon la revendication 2, dans lequel lesdits grains d'halogénure d'argent sont des grains de bromochlorure d'argent ayant une phase localisée à bromure d'argent dans laquelle la teneur en bromure d'argent est supérieure d'au moins 10% en moles à celle des autres portions.
  9. Matériau photosensible selon la revendication 8, dans lequel ladite phase localisée à bromure d'argent contient 10 à 60% en moles de bromure d'argent.
  10. Matériau photosensible selon la revendication 6, dans lequel lesdits grains à halogénure d'argent sont sensibilisés chimiquement avec un composé de l'or à raison d'une quantité de 1 à 10-8 à 1 x 10-2 mole par mole d'halogénure d'argent.
  11. Matériau photosensible selon la revendication 3, dans lequel lesdits grains de bromochlorure d'argent contiennent 95 à 99,9% en moles de chlorure d'argent.
  12. Matériau photosensible selon la revendication 3, dans lequel ladite phase riche en bromure d'argent possède une teneur en bromure d'argent supérieure d'au moins 10% en mole à celle des autres portions.
  13. Matériau photosensible selon la revendication 12, dans lequel ladite phase riche en bromure d'argent contient 10 à 60% en moles de bromure d'argent.
EP93108671A 1992-05-29 1993-05-28 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0572029B1 (fr)

Applications Claiming Priority (6)

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JP13940292 1992-05-29
JP139351/92 1992-05-29
JP13935192A JP2840500B2 (ja) 1992-05-29 1992-05-29 ハロゲン化銀カラー写真感光材料
JP13940292A JP2840501B2 (ja) 1992-05-29 1992-05-29 ハロゲン化銀カラー写真感光材料
JP13935192 1992-05-29
JP139402/92 1992-05-29

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US4791053A (en) * 1985-12-03 1988-12-13 Fuji Photo Film Co., Ltd. Silver halide photographic material
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US5378594A (en) * 1990-09-18 1995-01-03 Fuji Photo Film Co., Ltd. Silver halide color photographic material
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